This invention relates to novel compounds of N-substituted or non-substituted benzoyl-N'-trichloroethylidene hydrazine which may be expressed by the following general formula: ##STR2## WHEREIN R or R' stands for H, halogen atom, EQU CH.sub.3, OH, OCH.sub.3 or NO.sub.2.
it further relates to novel agricultural and horticultural fungicides having, as their effective substance, at least one of the said chemical compounds.
Various and numerous compounds are hitherto known which are originated from substituted benzoyl hydrazine. Certain reaction products of substituted benzoyl hydrazine with chloral are also known. As an example, N-benzoyl-N'-trichloroethylidene hydrazine is already described in literature [refer to Journal of Pharmaceutical Society of Japan, 85(3), 181(1965)].
In addition N-2-chlorobenzoyl-N'-trichloroethylidene hydrazine is also known [refer to Chem. Absts. 47, 3929a(1953)]. Further, 4-methyl and 4-nitro-derivatives are also known [refer to Chem. Absts. 67. 73299.times.(1967)].
However, it should be noted that these descriptions relate exclusively to the reaction steps and do not refer to any fungicidal function of these compounds in agricultural and horticultural purposes.
A careful and profound screening study of these known N-substituted and non-substituted benzoyl-N'-trichloroethylidene hydrazine derivatives and novel derivatives synthesized by our selves for the first time, we have found that those selected and found by ourselves have, indeed, remarkable agricultural and horticultural fungicidal effects.
In the following table, our inventive compounds are listed:
Table 1 __________________________________________________________________________ No. Structural formula Nomination m.p., .degree. C. Yield, % __________________________________________________________________________ 1 ##STR3## N-benzoyl- N'-(2,2,2- trichloro- ethylidene) hydrazine 194- 5 (decom- position) 81 2 ##STR4## N-2-chloro- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 183- 4 (decom- position) 67 3 ##STR5## N-4-methyl- benzoyl-N'- (2,2,2-tri- chloroethyl- lidene)hydra- zine 172- 3 (decom- position) 48 4 ##STR6## N-4-nitro- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 169- 71 (decom- position) 51 5 ##STR7## N-2-bromo- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 186- 8 (decom- position) 82 6 ##STR8## N-3-bromo- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 158- 9 (decom- position) 55 7 ##STR9## N-4-bromo- benzoyl-N-'- (2,2,2-tri- chloroethy- lidene)hydra- zine 184- 5 (decom- position) 14 8 ##STR10## N-3-chloro- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 149- 50 (decom- position) 60 9 ##STR11## N-4-chloro- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 157- 9 (decom- position) 43 10 ##STR12## N-2-fluoro- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 185- 6 (decom- position) 36 11 ##STR13## N-3-fluoro- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 179- 80 (decom- position) 82 12 ##STR14## N-4-fluoro- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 164- 5 (decom- position) 78 13 ##STR15## N-2-hydro- xybenzoyl- N'-(2,2,2- trichloro- ethylidene) hydrazine 184- 5 (decom- position) 89 14 ##STR16## N-4-hydro- xybenzoyl- N'-(2,2,2- trichloro- ethylidene) hydrazine 221- 3 (decom- position) 85 15 ##STR17## N-2-iodo- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 203- 4 (decom- position) 82 16 ##STR18## N-3-iodo- benzoyl-N'- (2,2,2-tri- chloroethyl- lidene)hydra- zine 162- 3 (decom- position) 37 17 ##STR19## N-4-iodo- benzoyl-N' (2,2,2-tri- chloroethy- lidene)hydra- zine 183- 4 (decom- position) 20 18 ##STR20## N-2-metho- xybenzoyl- N'-(2,2,2- trichloro- ethylidene) hydrazine 122- 3 60 19 ##STR21## N-4-metho- xybenzoyl- N'-(2,2,2- trichloro- ethylidene) hydrazine 163- 4 (decom- position) 33 20 ##STR22## N-2-methyl- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 191- 2 (decom- position) 40 21 ##STR23## N-3-methyl- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 160- 1 (decom- position) 39 22 ##STR24## N-2-nitro- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 167- 8 (decom- position) 77 23 ##STR25## N-5-chloro- 2-hydroxy- benzoyl-N'- (2,2,2-tri- chloroethy- lidene)hydra- zine 184- 6 (decom- position) 73 24 ##STR26## N-2-chloro-4- nitrobenzoyl- N'-(2,2,2-tri- chloroeth yli- dene)hydrazine 170- 1 (decom- position) 83 25 ##STR27## N-2,4-dichlo- robenzoyl-N'- (2,2,2-trichlo- roethylidene) hydrazine 181- 2 (decom- position) 70 26 ##STR28## N-2,5-dichlo- robenzoyl-N' (2,2,2-trichlo- roethylid ene) hydrazine 167- 8 (decom- position) 57 27 ##STR29## N-3,4-dichlo- robenzoyl-N'- (2,2,2-trichlo- roethylidene) hydrazine 170- 1 (decom- position) 42 28 ##STR30## N-3,4-dime- thoxybenzoyl- N'-(2,2,2- trichloroethy- idene)hydra- zine 218- 20 (decom- position) 25 29 ##STR31## N-3,5-dinitro- benzoyl-N'- (2,2,2-trichloro- ethylidene) hydrazine 191- 2 (decom- position) 68 __________________________________________________________________________ Remarks: Compounds 1- 4 are known and Compounds 5- 29 are unknown.
For the preparation of the foregoing compounds, the procedure may follow substantially in the following reaction: ##STR32## wherein R or R' stands for H, halogen, CH.sub.3, OH, OCH.sub.3 or NO.sub.2 ;
Or, more specifically, the corresponding acid hydrazide and chloral are refluxed in benzene for 1-3 hours easily to form the desired corresponding product.